Process of modifying textile materials with polymerizable monomers

ABSTRACT

A textile material is reacted with unsaturated, polymerizable compounds in the presence of a reaction catalyst in a process wherein the reactive material and the catalyst are contained in a liquid medium and the weight ratio between the liquid medium and the textile material is less than 25/1.

United States Patent Machell et a1.

1451 Sept. 30, 1975 1 PROCESS OF MODIFYING TEXTILE MATERIALS wrrn POLYMERI ZABLE MQNOMERS [75] lnventors: Greville Machell; Manuel A.

Thomas, both of Spartanburg. SC.

[73] Assignee: Deering Milliken Research Corporation, Spartanburg. SC.

[22] Filed: Dec. 6, 1962 1211 Appl. No.: 242,603

152] US. Cl. 8/11'5.7; 8/120; 8/129;

8/1275; 8/1276; 8/128 A; 8/128 R; 8/129; 8/189: 8/193; S/DIG. 4; 8/D1G. 18; 8/DIG. 21 [51] Int. Cl. D0 M 15/36; D06M 15/38; D06M 15/32 [58] Field of Search 8/D1G.18. 127.5. 127.6. 8/128 R, 128 A,l29,193,120,115.7; 117/141.143 A,145. 155 UA,161UZ, 161 VA.161 UB. 161 UP, D1G.3

[561 References Cited UNITED STATES PATENTS 2.732.317 1/1956 Kirby 8/D1G. 18 2.764.504 9/1956 Jacobson et a1. 8/D1G. 18

Prinmry Eraminer-George F. Lesmes Assistant l-Lruminer-J. Cannon Attorney, Agent, or Firtn--Arthur L. Urban; H. William Petty [57] ABSTRACT A textile material is reacted with unsaturated, polymerizable compounds in the presence of a reaction catalyst in a process wherein the reactive material and the catalyst are contained in a liquid medium and the weight ratio between the liquid medium and the textile material is less than 25/ 1.

10 Claims. No Drawings PROCESS OF MODIFYING TEXTILE MATERIALS WITH POLYMERIZABLE MONOMERS This invention relates to an improved process for reacting textile fibers with ethylenically unsaturated compounds.

Reactions between textile fibers and ethylenically unsaturated compounds have been conducted for a variety of reasons, for example, for shrinkproofing, modification of dyeing properties and the like. These reactions are generally characterized by fairly poor monomer conversion, necessitating a long period of time to conduct the reaction in order to'obtain the desired level of pickup of reacted material.

It is an object of this invention to provide a process improvement whereby the efficiency of reactions between textile fibers and ethylenically unsaturated compounds is radically improved.

These objects are accomplished in accordance with this invention by conducting the reaction in a liquid medium wherein the weight ratio of liquid to textile fibers is less than about 25 to 1, preferably less than about to 1. By conducting the desired reaction at these lower bath ratios, the initial monomer concentration in the reaction bath is increased, and the necessary reaction time for excellent monomer conversion and high pickup of the reacted ethylenically unsaturated compound on the fiber is greatly reduced. In addition, even though there is more reacted material obtained in less time, there is less homopolymer formation than is generally experienced at higher bath ratios.

Ethylenically unsaturated compounds can be reacted with textile fibers, particularly keratin and cellulosic fibers, through a number of well-known processes, all of which may be utilized to conduct the process improvement of this invention. For example, these fibers may be reacted with the desired compound in the presence of a catalyst or initiator system for inducing polymerization of the compound. Among such systems there areincluded azo catalysts, such as azobisisobutyronitrile, as well as the redox catalyst systemscomposed of a reducing agent and an oxidizing agent initiator. Although the catalytic mechanism is not completely understood, it is believed that the interaction of these agents provides free radicals encouraging polymerization of the compounds, which preferably are in monomeric or low polymeric form, onto the fibers. This latter type initiating system is preferred when the process improvement is conducted on keratin fibers.

The reducing agent may be an iron compound such as the ferrous salts, including ferrous sulfate, acetate,

phosphate, ethylenediamine tetra-acetate; metallic formaldehyde sulfoxylates, such as zinc formaldehyde sulfoxylate; alkali-metal sulfoxylates, such as sodium formaldehyde sulfoxylate; alkali-metal sulfites, such as sodium and potassium bisulfite, sulfite, metabisulfite or hydrosulfite; mercaptan acids, such as thioglycollic acid and its water-soluble salts, such sodium, potassium or ammonium thioglycollate; mercaptans, such as hydrogen sulfide and sodium or potassium hydrosulfide; alkyl mercaptans, such as butyl or ethyl mercaptans; and mercaptan glycols, such as beta-mercaptoethanol: alkanolamine sulfites, such as monoethanolamine sulfite and mono-isopropanolamine sulfite; manganous and chromous salts; ammonium bisulfite; sodium hydrosulfide; cysteine hydrochloride; sodium thiosulfate; sulfur dioxide; sulfurous acid and the like, as well as mixtures of these reducing agents. In addition, a salt of hydrazine may be used as the reducing agent, the acid moiety of the salt being derived from any acid, such as hydrochloric, hydrobromic, sulfuric, sulfurous, phosphoric, benzoic, acetic and the like.

Suitable oxidizing agent initiators for use in the redox catalyst system include inorganic peroxides, e.g., hydrogen peroxide, barium peroxide, magnesium peroxide, etc., and the various organic peroxy catalysts, illustrative examples of which are the dialkyl peroxides, e.g., diethyl peroxide, dipropyl peroxide, dilauryl peroxide, dioleyl peroxide, distearyl peroxide, di-(tert.- butyl) peroxide and di-(tert.-amyl) peroxide, such per- .oxides often being designated as ethyl, propyl, lauryl,

oleyl, stearyl, tert.-butyl and tert.-amyl peroxides; the alkyl hydrogen peroxides, e.g., tert.-butyl hydrogen peroxide (tert.-butyl hydroperoxide), tert.-amyl hydrogen peroxide (tert.-amyl hydroperoxide), etc.; symmetrical diacyl peroxides, for instance peroxides which commonly are known under such names as acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinyl peroxide, phthaloyl peroxide, benzoyl peroxide, etc.; fatty oil acid peroxides, e.g., coconut oil acid peroxides, etc.; unsymmetrical or mixed diacyl peroxides, e.g., acetyl benzoyl peroxide, propionyl benzoyl peroxide, etc.; terpene oxides, e.g., ascaridole, etc.; and salts of inorganic peracids, e.g., ammonium persulfate,-potassium persulfate, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium perphosphate, potassium perphosphate, etc.

Other examples of organic peroxide initiators that can be employed are the following: tetralin hydroperoxide, tert.-butyl diperphthalate, cumene hydroperoxide, tert.-butyl perbenzoate, 2,4-dichlorobenzoyl peroxide, urea peroxide, caprylyl peroxide, pchlorobenzoyl peroxide, 2,2-bis(tert.-butyl peroxy) bu tane, hydroxyheptyl peroxide, diperoxide of benzaldehyde and the like.

The above oxidizing agents, particularly the salts of inorganic peracids, may be utilized alone to initiate the graft polymerization process, although faster reactions at lower temperatures may be conducted when the oxidizing agent is combined with a reducing agent to form a redox catalyst system. Ferric salts can be used as oxidizing agents and form a redox catalyst system with hydrogen peroxide, in which case the peroxide functions as a reducing agent.

When cellulosic fibers are treated, the reaction may also be initiated by ceric ions, for example, in the form of ceric salts such as ceric nitrate, ceric sulfate, ceric ammonium nitrate, ceric ammonium sulfate, ceric ammonium pyrophosphatc, ceric iodate, and the like. This latter initiating system is preferred when the reaction is conducted on cellulosic fiber.

The reaction between these fibers and ethylenically unsaturated compounds most readily takes place in the presence of water. This generally presents no problem since only small amounts are necessary for this improvement and since the catalyst components and/or monomers are generally applied to the fibers in an aqueous medium. Ionic or non-ionic surface active agents may be utilized in any aqueous medium used in applying the reagents.

chlorostyrene,

bis(trifluo'romethyl) styrene, S-trifiuoromethylstyrene,.

tached to the molecule thereof, in that extraction techniques utilizing solvents for the homopolymer for such ethylenically unsaturated compounds fail to remove the reacted compound. That material which in some instances can be extracted from fibers treated by these techniques has been designated as homopolymer. It is realized, however, that some homopolymer may well be occluded or ionically bound within the interstices of the fibers and that not all of the polymeric material remaining on the substrate is covalently attached to the fibers, if indeed this is the reason the reacted material cannot be extracted from the fiber. For purposes of this invention, however, since neither the occluded nor the chemically attached polymer may be readily extracted from the keratin fiber, the term reacted polymer" is intended to include both types of non-extractible polymer. The process of this invention, however, may be utilized to produce fibers containing extractible reacted compounds, although these products are generally less preferred.

The above techniques may be utilized to react any ethylenically unsaturated compound with textile fibers. These compounds include N-dialkyl acrylamides, for example: N,N'-dimethyl, -diethyl, -dipropyl, -dibutyl, -diamyl, -dihexyl, -dioctyl, etc., acrylamides; N-(panisyl) methacrylamide, N-(p-chlorophenyl) methacrylamide, N-phenyl methacrylamide, N-ethylmethylmethacrylamide, N-methylmethacrylamide, N-(ptolyl) methacrylamide and the like; the acrylic, alphaalkyl acrylic and alpha-haloacrylic esters of saturated monohydric alcohols, for instance saturated aliphatic monohydric alcohols, e.g., the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, etc., esters of acrylic, methacrylic, ethacrylic, propacrylic, chloroacrylic, bromoa'crylic, aconitic, itaconic, maleic, crotonic, fumaric, etc.; acids; these latter type acids and anhydridesthereof; the phenyl, benzyl, phenylethyl, etc., esters of the aforementioned acids; vinyl aromatic compounds, e.g., styrene; methylstyrenes, such as m-, p-methylstyrene; dimethylstyrenes, such as 2,5- di rnethylstyrene; halogenated styrenes, such as mbromostyrene, p-bromostyrene, p-iodostyrene, pentaozfifi-trifluorostyrene, 2,5-

dichlorostyrene and the like; the various cyanostyrenes, the various methoxystyrenes, e.g., pmethoxystyrene vinyl naphthalenes, e.g., 4-chloro-lvinylnaphthalene, 6chloro-2-vinylnaphthalene, etc.; vinyl and vinylidene halides, e.g., vinyl and vinylidene chlorides, bromides, etc.; alkyl vinyl ketones, e.g., methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, etc.; itaconic and maleic diesters containing a single CH -$group,

e.g., the dimethyl, diethyl, di-B-chloroethyl, diethylchloro, dipropyl, diisopropyl, dibutyl and other saturated aliphatic monohydric alcohol diesters of itaconic and maleic acid, diphenyl itaconate and maleate,, dibenzyl itaconate and maleate, di-(phenylethyl) itaconate and maleate, etc.; vinyl, ally] and metallyl esters of saturated aliphatic monocarboxylic acids, e.g., vinyl, allyl and metallyl acetates, vinyl, allyl and metallyl propionates, vinyl, ally] and methallyl valerates, etc.; vinyl thiophene; vinyl pyridine; vinyl pyrrole; nitriles containing a single grouping, e.g., acrylonitrile, methacrylonitrile, etc.

The treatment of textile fibers in accordance with this'invention may be conducted at any desired temperature, although reactions in the presence of a redox catalyst system are preferably conducted at temperatures between about 40 and about 60C. A temperature in excess of about C is generally not preferred with this catalyst system since many of the components utilized in these systems degrade at elevated temperatures. In general, such conditions as concentrations of the reagents, pH, time and temperature may be modified to suit the individual circumstances and equipment utilized.

Improved results are obtained when the fibers are in a swollen condition during reaction. This condition is most readily obtained by conducting the reaction in the presence of a swelling agent for the fibers, in addition to the water normally used. For example, for keratin fibers urea; thiourea; lithium salts, such as the chloride, bromide and iodide; guanadine compounds, such as the hydrochlorides; amides, such as formamide, N ,N- dimethyformamide, acetamide, N,N- dimethylacetamide and the like may be utilized. For cellulosic fibers, swelling agents such as alkali-metal hydroxides, including sodium hydroxide and potassium hydroxide may be utilized.

While any desired equipment and technique of applying the reagents may be utilized, for example, padding, immersing or the like, the techniques described in copending and coassigned US. Patent application Ser. No. 243,671, now US. Pat. No. 3,291,560, are generally preferred. In the inventions described therein, package dye machinery is modified to provide increased flow rates whereby the reaction between keratin fibers and the ethylenically unsaturated compounds proceeds at an optimum rate in a particularly desirable manner.

Keratin fibers which may be treated in accordance with this invention include wool, mohair, alpaca, cashmere, vicuna, guanaco, camels hair, silk, llama and the like. Cellulosic fibers which may be treated in accordance with this invention include natural cellulosic fibers, for example, cotton, paper, linen, jute, flex; regenerated cellulose fibers, for example, viscose rayon; fibers containing a limited number of acetyl groups, such as cellulose acetate; fibers which contain a limited number of methylether groups, such as partially methylated cellulose and the like.

These fibers may be blended with synthetic or other natural fibers. The preferred synthetic fibers include polyamides, such as poly(hexamethylene adipamide); polyesters, such as poly(ethylene terephthalate), and acrylic fibers, such as acrylonitrile homopolymer or copolymers containing at least about 85% combined acrylonitrile, such as acrylonitrile/methylacrylate (85/15'). In the following Examples, except where noted, each wool sample is scoured by immersing in or passing therethrough an aqueous solution containing 0.5% on the weight of wool of Sulfonic N-95, a non-ionic surface active agent and 1.5% on the weight of wool of glacial acetic acid. After scouring for 20 minutes at F,

the sample is rinsed in water at 100F for l0l5 minutes. Deionized water is used in preparing all aqueous media.

EXAMPLE 1 Into a 2-lb. Gaston County package dyeing machine are mounted 800 gms. of wool top, 400 gms. being mounted on each of 2 bobbins which are placed on the single perforated spindle of the dye machine. After scouring and rinsing, an aqueous solution made up from 7400 ccs of water, 1.74 gms. Fe(NO .9H O (0.03% Fe based on the wool weight), 12.2 ccs of a 50% solution of H 0 (50/1 molar ratio of peroxide based on Fe**), and 40 ccs of concentrated 1-1 80 is circulated through the machine and the wool top. After ten minutes, 960 gms. of acrylonitrile, enough for 120% pickup, are added to the recirculating-catalyst system. The resulting system has a pH of 1.3 and provides a liquor/wool ratio of 1 1.1. The liquor is adjusted to provide liquor/wool ratios of 30/1, 19/1 and 8/1 as set forth in Table 1. Each of these systems is run follows:

Each system is then held at 7585F and forced back and forth through the fibers at a flow rate of about 35 gallons per minute for minutes, at a cycle of 3 minutes outside-in and 2 minutes inside-out. By outsidein is meant that the system is forced from the outside of the wook top package into the perforated spindle and through a recirculating system back to the outside of the wool top package. In the inside out flow pattern, this procedure is reversed.

The temperature is then increased at 120F and the reaction is continued at this temperature for an addi tional 105 minutes. The wool top is removed from the machine and found to have increased in weight by the levels shown in Table I.

The improvement in the process is quite apparent from the data in Table 1.

EXAMPLE 11 Under the same variations of bath ratios and reaction time as in Example 1, substantially similar improvement in the per cent weight increase and per cent monomer conversion is noted when acrylonitrile is reacted with cotton yarns (6s).

That which is claimed is:

1. A novel process for reacting textile fibers with ethylenically unsaturated compounds comprising:

1. providing an ethylenically unsaturated compoundcontaining liquid medium;

2. providing textile fibers, the weight ratio of the liquid medium to the textile fibers being between about 8/1 and about 20/1;

3. forcing said liquid medium back and forth through said textile fibers in the presence of a chemical, textile fiber reaction promoting catalyst;

4. and withdrawing said textile fibers from said liquid medium after permitting the desired degree of reaction to occur; said textile fibers comprising keratinic fibers, cellulosic fibers or blends of either keratinic or cellulosic fibers with acrylic fibers, synthetic polyamide fibers or synthetic polyester fibers.

2. The process of claim 1 wherein the process is conducted in an aqueous medium containing a ceric ion.

3. The process of claim 1 wherein the textile fibers are in substantially loose form during contact with the liquid medium.

4. The process of claim 1 wherein the catalyst comprises a redox catalyst system.

5. The process of claim 4 wherein the redox catalyst system comprises an iron compound.

6. The process of claim 4 wherein the redox catalyst system further comprises a peroxide.

7. The process of claim 1 wherein the liquid medium is aqueous.

8. The process of claim 7 wherein the textile fibers are keratinous.

9. The process of claim 7 wherein the textile fibers are cellulosic.

10. The process of claim 9 wherein the cellulosic fiber comprises cotton. 

1. A NOVEL PROCESS FOR REACTING TEXTILE FIBERS WITH ETHYLENICALLY UNSATURATED COMPOUNDS COMPRISING:
 1. PROVIDING AN ETHYLENICALLY UNSATURATED COMPOUND-C/NTAINING LIQUID MEDIUM:
 2. PROVIDING TEXTILE FIBERS, THE WEIGHT RAATIO OF THE LIQUID MEDIUM TO THE TEXTILE FIBERS BEING BETWEEN ABOUT 8/1 AND ABOUT 20/1:
 2. providing textile fibers, the weight ratio of the liquid medium to the textile fibers being between about 8/1 and about 20/1;
 2. The process of claim 1 wherein the process is conducted in an aqueous medium containing a ceric ion.
 3. The process of claim 1 wherein the textile fibers are in substantially loose form during contact with the liquid medium.
 3. forcing said liquid medium back and forth through said textile fibers in the presence of a chemical, textile fiber reaction promoting catalyst;
 3. FORCING SAID LIQUID MEDIUM BACK AND FORTH THROUGH SAID TEXTILE FIBERS IN THE PRESENCE OF A CHEMICAL, TEXTILE FIBER REACTION PROMOTING CATALYST:
 4. AND WITHDWAWING SAID TEXTILE FIBERS FROM SAID LIQUID MEDIUM AFTER PERMITTING THE DESIRED DEGREE OF REACTION TO OCCUR: SAID TEXTILE FIBERS COMPRISING KERATINIC FIBERS, CELLULOSIC FIBERS OR BLENDS OF EITHER KERATINIC OR CELLULOSIC FIBERS WITH ACRYLIC FIBERS, SYNTHETIC POLYAMIDE FIBERS OR SYNTHETIC POLYESTER FIBERS.
 4. and withdrawing said textile fibers from said liquid medium after permitting the desired degree of reaction to occur; said textile fibers comprising keratinic fibers, cellulosic fibers or blends of either keratinic or cellulosic fibers with acrylic fibers, synthetic polyamide fibers or synthetic polyester fibers.
 4. The process of claim 1 wherein the catalyst comprises a redox catalyst system.
 5. The process of claim 4 wherein the redox catalyst system comprises an iron compound.
 6. The process of claim 4 wherein the redox catalyst system further comprises a peroxide.
 7. The process of claim 1 wherein the liquid medium is aqueous.
 8. The process of claim 7 wherein the textile fibers are keratinous.
 9. The process of claim 7 wherein the textile fibers are cellulosic.
 10. The process of claim 9 wherein the cellulosic fiber comprises cotton. 